Austenitic steel with improved high-temperature strength and corrosion resistance

ABSTRACT

Austenitic steel with improved high-temperature strength and corrosion resistance, characterized by the simultaneous presence, in defined quantities, of Nb, Mo and V and by the presence of C and N in a specific ratio with said three elements.

DESCRIPTION

The object of this invention is an austenitic steel with improved hightemperature strength and corrosion resistance. Austenitic steels areknown either characterized by very low Ni contents (not exceeding 2% byweight)--as described in GB Patent 1 108 384 --or containing no Ni atall (GB 834 218). However, such steels show poor high-temperatureproperties, because of a certain amount of hot brittleness, butespecially because of their low resistance to high temperature oxidationand sulphidation. Also steels are known having a high Ni content(between 2 and 10% by weight), such as commercially available EMS 235which, though having better oxidation and sulphidation resistance thanthose mentioned above, have poor high-temperature creep performance.

Improvements of such properties have been obtained modifying the abovealloys by the addition of further elements such as Mo or W or others,for instance Pertinent in this respect is U.S. Pat. No. 3,969,109 whichclaims a steel composition basically containing C, Mn, Cr, Ni and N, towhich at least one or more of the following elements can be added, ifnecessary: Mo up to 4% by weight, W up to 3% by weight and Nb and/or Vup to 2% by weight.

However, of the alloys examined in that patent, those with the bestproperties contain none of said optional elements. Moreover the onealloy examined containing more than one of these elements is inferior toothers as regards high-temperature oxidation and sulphidationperformance.

Moreover, none of said modified steels can ensure long-term constancy ofstrength and corrosion resistance, especially at temperature in excessof 450° C., since formation of σ phase is possible, which increaseshardness and wear resistance of the steel, but lowers ductility,toughness and corrosion resistance.

It is also possible for such steels to have dual phaseaustenite-martensite or austenite-ferrite structures in the solubilizedand aged state. Such dual phase structures are harmful when present inthe solubilized state, since they reduce the hot workability of thesteel. When such dual phase structures are present in the solubilizedand aged state, they impair mechanical properties of the steel.

As a consequence austenitic steels having better properties, especiallyfor high-temperature applications were needed. Since temperatures of800°-900° C. and possibly very high temperature gradients, for instanceof 150° C., can be present in modern engineering applications, steelswere required having good mechanical properties combined with bettercorrosion resistance, especially at high temperatures, and producible ata reasonable price.

Moreover, it was important that said steels maintain nearly constant intime the improved properties to extend their useful life under suchconditions.

Surprisingly it has been found that the simultaneous presence of V, Nband Mo in specific, well-defined quantities allows to produce an alloysteel showing none of the defects listed above. The object of thisinvention is to provide an austenitic steel which, owing to thesimultaneous presence of Mo, V and Nb in a well-defined concentrationrange, and together with suitable quantities of C and N, possesses goodmechanical properties and also exceptional resistance tohigh-temperature corrosion, even up to 850° C. and beyond. Anotherobject of this invention is to provide a steel having reasonableproduction costs, owing to the small quantity of expensive elements init.

Yet another object of the invention is to provide a steel whichmaintains aforesaid improved properties nearly constant for aconsiderable extent of time, thus ensuring long, reliable life formechanical parts made from it.

Still a further object of the invention is to provide a solubilizationand aging treatment for the steel of the invention so that its improvedproperties can be fully exploited.

The steel according to the present invention is characterized by acomposition (in % by weight) comprising the following elements:

0.40-0.65 carbon

0.35-0.60 nitrogen

2.0-3.0 manganese

22.0-24.0 chromium

7.5.-8.5 nickel

0.7-1.3 molybdenum

0.6-1.2 vanadium

0.7-1.5 niobium

up to 0.3 silicon

up to 0.03 sulphur

up to 0.025 phosphorus

balance essentially iron.

A preferred composition (in % by weight) for steel of the inventioncomprises the following elements:

0.59-0.63 carbon

0.45-0.60 nitrogen

2.0-3.0 manganese

22.0-24.0 chromium

7.5-8.5 nickel

0.8-1.1 molybdenum

0.8-1.1 vanadium

0.8-1.2 niobium

≦0.3 silicon

≦0.03 sulphur

≦0.025 phosphorus

balance essentially iron.

The composition of the steel according to the invention is characterizedby a specific ratio among the constituent elements. Particularly, it ischaracterized by the simultaneous presence in definite quantities of Mo,V and Nb which are linked through a specific ratio to the quantity of Cand N present in the alloy. Such specific ratio is expressed by thefollowing mathematical relations, where the elements are expressed inatomic fractions:

(A) (Nb+V)/(C+N)=0.25-0.45

(B) N/C=0.6-1.1

(C) V/Nb=0.5-2.0

(D) Mo/C=0.15-0.25.

It has been found that the simultaneous presence of Mo, V and Nb inspecific quantities improves the mechanical properties of the steel,such as hardness and creep resistance at low and high temperatures, forinstance, it also increases corrosion resistance in oxidizing andsulphurizing atmospheres at high temperatures (about 800°-900° C. andabove).

Moreover, the specific ratio linking C and N to said three elements (Mo,V and Nb) results in a steel whose improved properties remain nearlyconstant for a long time under service conditions. The composition ofthe steel according to the invention is balanced in order to increasethe contribution of each element of the alloy so that the interactionsoccurring between them, which however are always difficult to foresee,can improve the overall properties of the steel concerned.

To explain the difficulty of a priori prediction of the behaviour of analloy, U.S. Pat. No. 3,969,109 can be mentioned, in which a possiblenon-specific addition of some elements selected from Mo, V, Nb and W tothe alloy worsened its high-temperature behaviour in oxidizing andsulphidizing atmospheres. (see Table II of cited Patent). Here it hasbeen found that the above elements can be suitably combined so that notonly mechanical properties are improved when compared with knowncomposition, but also behaviour of the alloy in aggressive environmentsand at high temperatures is improved, even in prolonged serviceconditions, as stated above.

V, Nb and Mo have been combined so that, within the limits ofconcentration defined by the mathematical relations already given, nodual-phase structures occur in the alloy either in the solubilized or inthe solubilized and aged states. The steel according to the inventioncan be unworked thereby avoiding harmful dual phase structurescharacterized by anisotropic behaviour in hot deformation and by atendency to form microcracks and internal defects. The hardening effectresults from a specific volume fraction of Nb and V carbides and a Mofraction present in solid solution so as not to increase the ductilityof the material.

The composition so obtained does not give rise to σ phase, so the steelaccording to the invention is stable for a long time under hightemperature service conditions, as already mentioned. According to thepresent invention, in addition to a carefully thought out composition,it is very important to select a suitable, specific solubilizing andaging treatment which ensures the best microstructure for the servicerequirements of the steel. Solubilizing treatment is performed at atemperature between 1130° and 1230° C. for between 0.2 and 3 hours, thehighest treatment temperatures involving the lower time limits of therange indicated, while the longer times referring to treatments at thelower temperatures of the range.

Preferred solubilizing condition is 1170°-1190° C. respectively for1-0.5 h followed by rapid cooling, preferably water cooling. In thesolubilized state, the steel consists of a completely austenitic matrixin which carbides of Nb containing V and carbides of Cr, Mo and V aredispersed.

Aging treatment consists in holding the steel from 0.5 to 40 hours attemperatures of between 870° and 650° C. respectively, followed by aircooling. The preferred condition is: 740°-820° C. respectively for20-4h. Even more preferable is the 740°-760° C. temperature range for18-6 hours respectively. During aging precipitation of very finecarbides occurs, which are dispersed in the matrix and on the grainboundaries.

The steel according to the invention is used for those mechanical partswhich must work under high continuous mechanical stress in corrosiveenvironments, for instance in oxidizing or sulphidizing atmospheres orthe presence of molten salts and at temperatures up to 900° C. and more.

The steel of the invention performs well under test as valves fornormally aspirated and supercharged gasoline and diesel engines,precombustion chambers for diesel engines, parts for turbine engines andparts in chemical plants that are subject to high temperature stressesand corrosive environments.

Some characterization test performed on a steel composition as per thisinvention are outlined in the following tables where the results arecompared with those for state-of-the art steels. The results merelyprovide an indication of the characteristics of the steel of theinvention, and should not be considered a limitation on the inventionitself.

                  TABLE 1                                                         ______________________________________                                        Compositions (% weight) examined                                                     VA                                 VA   VA                                    70     033040  8976 8975 8974 8968 63   62                             Element                                                                              *      **      **   **   **   **   ***  ***                            ______________________________________                                        C      0.60   0.35    0.40 0.41 0.33 0.40 0.53 0.72                           N      0.45   0.42    0.30 0.35 0.30 0.35 0.45 0.25                           Mn     2.39   1.81    1.83 1.81 1.72 1.74 9.0  6.30                           Cr     22.55  24.50   22.03                                                                              22.23                                                                              21.93                                                                              21.93                                                                              21.0 21.0                           Ni     7.97   5.83    8.79 1.60 6.78 6.68 4.0  1.70                           Mo     1.06   --      --   --   1.89 2.04 --   --                             V      0.99   --      --   --   --   --   --   --                             Nb     1.09   --      --   0.29 0.29 --   1.8  --                             W      --     --      --   --   --   --   0.9  --                             Si     0.27   0.29    0.50 0.53 0.57 0.57 0.3  0.6                            S      0.005  0.011   0.014                                                                              0.016                                                                              0.016                                                                              0.017                                                                              0.025                                                                              0.025                          P      0.022  0.012   0.016                                                                              0.017                                                                              0.026                                                                              0.027                                                                              0.03 0.03                           ______________________________________                                         * Composition of the present invention                                        ** Composition given for comparison (U.S. Pat. No. 3,969,109)                 *** Composition given for comparison                                     

                  TABLE 2                                                         ______________________________________                                        Mechanical properties at room temperature                                                         0.2% TYS                                                          UTS (MPa)   (MPa)      A (%)  Z (%)                                   Steel   (a)         (b)        (c)    (d)                                     ______________________________________                                        VA 70*  1085        668        20     13                                      033040**                                                                              1043        670        15     11                                      8976**   971          527.5      24.5   31.8                                  8975**   972        534          26.5 29                                      8974**  1007        582        24       25.5                                  8968**   675        449        n.d.   n.d.                                    VA 63***                                                                              1070        620        17     16                                      VA 62***                                                                              1020        610        14     18                                      ______________________________________                                         *Steel of the present invention                                               **Steel for comparison (U.S. Pat. No. 3,969,109)                              ***Steel for comparison                                                       (a) Ultimate Tensile Strength (UTS)                                           (b) Tensile Yield Strength (TYS)                                              (c) Percent elongation at rupture (A)                                         (d) Percent reduction of area at rupture (Z)                                  n.d. Not determined                                                      

                                      TABLE 3                                     __________________________________________________________________________    Mechanical properties at high temperature                                                  0.2% TYS                                                         UTS (MPa)    (MPa)   A (%)   Z (%)   Brinell                                  (a)          (b)     (c)     (d)     hardness                                 Steel                                                                              760° C.                                                                    872° C.                                                                    760° C.                                                                    872° C.                                                                    760° C.                                                                    872° C.                                                                    760° C.                                                                    872° C.                                                                    760° C.                                                                    872° C.                       __________________________________________________________________________    VA 70                                                                              518 434 x                                                                             374 299 x                                                                             18.5                                                                              18.9 x                                                                            33.4                                                                              32.7 x                                                                            166 158                                  *        350     260     20.0    33.0                                         033040                                                                             472 325 291 223 17.9                                                                              17.1                                                                              25.8                                                                              24.4                                                                              190 182                                  **                                                                            __________________________________________________________________________     * Same meaning as Table 2                                                     ** Same meaning as Table 2                                                    (a), (b), (c), (d) Same meaning as Table 2                                    x Figure obtained at 815° C.                                      

                  TABLE 4                                                         ______________________________________                                        Creep strength at 815° C.                                                            815° C.                                                         Steel  (e)                                                             ______________________________________                                               VA 70* 95                                                                     033040**                                                                             85.2                                                                   8976** 74.5                                                                   8975** 87.6                                                                   8974** 84.1                                                                   8968** 77.2                                                            ______________________________________                                         *Same meaning as Table 2                                                      **Same meaning as Table 2                                                     (e) Load for 1% creep in 100 hours at 815° C.                     

Table 1 sets forth compositions of the steels subjected to mechanicalstrength and corrosion resistance tests.

VA 70 is the steel according to the present invention

VA 62 and VA 63 are comparative steels because of their high Mn content

033040, 8976, 8975, 8974 and 8968 are numbers related tostate-of-the-art steels (U.S. Pat. No. 3,969,109).

Before testing, the steels were treated in the following manner:Solubilization at 1190° C. for one hour, followed by water quenching,then aging at 760° C. for sixteen hours. Table 2 shows the results ofmechanical strength properties at room temperature of VA 70, the steelof the invention compared with other steels of different composition.Taken as a whole, the mechanical properties of VA 70 are better thanthose of the other steels. Only 03340 has similar 0.2 percent TYS while8976, 8975 and 8974 behave better only as regards ductility at rupturein A and Z tension tests.

Comparison of the high-temperature strengths of VA 70 and 033040 (Tables3 and 4) shows the worse performance of the latter, only the hardnessbeing better; however, this could be the sign that Type 033040 steelstend to form σ phase, as already mentioned, which leads to a rapiddecrease of properties.

Table 4 shows the high creep strength of VA 70 compared with the othersteel tested.

So, the mechanical strength properties of the steel according to theinvention (VA 70), are better than those of other state-of-the-artsteels.

Oxidation tests were run by keeping the steel specimens for one hundredhours in a muffle in air atmosphere.

                  TABLE 5                                                         ______________________________________                                        Oxidation resistance at 872° C. for 100 hours                                 Steel   Δg/dm.sup.2 h                                            ______________________________________                                               VA 70*  0.147                                                                 033040**                                                                              0.456                                                                 8976**  0.697                                                                 8975**  0.718                                                                 8974**  0.743                                                                 8968**  0.702                                                                 VA 63***                                                                              0.171                                                                 VA 62***                                                                              0.646                                                          ______________________________________                                         *Same meaning as Table 2                                                      **Same meaning as Table 2                                                     ***Same meaning as Table 2                                               

Corrosion tests were run by placing the steel specimens in aluminacrucibles. Atmospheres and test conditions adopted were as follows:

(f) Lead oxide: 1h at 913° C.

This simulates the ash formed in internal combustion engines running onleaded gasoline (g) Sodium sulphate 90%+sodium chloride 10% 1 h at 927°C.

This simulates ash formed in diesel engines operating in a marineenvironment

(M) Calcium sulphate 55%, barium sulphate 30%, sodium sulphate

10%, carbon 5%: 1 h at 927° C.

This simulates ash formed in diesel engines

(n) Sodium sulphate 85%, vanadium pentoxide 15%: 1 h at 927° C.

This simulates the ash formed in fuels that contain vanadium

The steels tested had been solubilized and aged as described previously,the aging being performed at 760° C. for sixteen hours.

                  TABLE 6                                                         ______________________________________                                        Corrosion resistance (g/m.sup.2 · h)                                                  Na.sub.2 SO.sub.4 +                                                                      Sulphates +                                                                            Na.sub.2 SO.sub.4 +                      Steel   PbO (f)  NaCl (g)   C (m)    V.sub.2 O.sub.5 (n)                      ______________________________________                                        VA 70*  2390     51          77      49                                       8976**  5810     240         93      81                                       VA 63***                                                                              2325     catastrophic                                                                             111      74                                       VA 62***                                                                              6360     31         110      84                                       ______________________________________                                         */**/***/ Same meaning as Table 2                                        

The oxidation and corrosion resistance properties of the steel accordingto the present invention are overally better than those of known steels.

As can be seen from Table 5, the tests run in different environmentssimulating use in various kinds of engines reveal that VA 70 has betterproperties than the other steels. In detail:

in PbO the corrosion rate is slow and would indicate good possibilitiesfor using the steel of the invention for the construction of gasolineengine components

in the sodium sulphate/chloride mixture, the rate of corrosion is low;only VA 62 behaves better, the rate being much higher with the othersteels. The new steel thus has good possibilities for use in marinediesel engines

in the other corrosive environments (mixture of sulphates and carbon,and mixture of sodium sulphate and vanadium pentoxide), though there isno great difference in behaviour of the various steels. VA 70 stillperforms better than the steels with which it was compared.

To simulate the effect of prolonged high-temperature use of the steel,it was subjected to a temperature of 760° C. for one thousand hours. Theinfluence of this heat treatment on the behaviour of steels subjected tothe action of various corrosive environments was thus studied. Theresults are set forth in Table 7.

                  TABLE 7                                                         ______________________________________                                        Corrosion resistance of steel specimens held at 760° C.                for one thousand hours (g/m.sup.2 · h)                                       Na.sub.2 SO.sub.4 +                                                                      Sulphates + C                                              Steel   NaCl (g)   (m)         Na.sub.2 SO.sub.4 + V.sub.2 O.sub.5            ______________________________________                                                                       (n)                                            VA 70*  48          80         50                                             8976**  4150        86         77                                             VA 63** 207        108         62                                             VA 62***                                                                              65         104         80                                             ______________________________________                                         */**/***Same meaning as Table 2                                          

We claim:
 1. Austenitic steel with improved and long-term constant high-temperature strength and resistance to aggressive agents, .[.comprising.]. .Iadd.consisting essentially of .Iaddend.the following elements in % by weight:0.40-0.65 carbon 0.35-0.60 nitrogen .[.2.0-3.0 manganese.]. .Iadd.about 2.30 manganese .Iaddend. 22.0-24.0 chromium 7.5-8.5 nickel
 0. 7-1.3 molybdenum0.6-1.2 vanadium 0.7-1.5 niobium up to 0.3 silicon up to 0.03 sulphur up to 0.025 phosphorus balance essentially iron, carbon, nitrogen, vanadium, molybdenum and niobium being intercorrelated by specific ratios, said specific ratios being expressed in atomic fractions through the following mathematical relations:(A) Nb+V/C+N=0.25-0.45 (B) N/C=0.60-1.10 (C) V/Nb=0.50-2.0 (D) Mo/C=0.15-0.25. .Iadd.
 2. Austenitic steel with improved and long-term constant high-temperature strength and resistance to aggressive agents, comprising the following elements in % by weight:0.40-0.65 carbon 0.35-0.60 nitrogen about 2.39 manganese 22.0-24.0 chromium 7.5-8.5 nickel 0.7-1.3 molybdenum 0.6-1.2 vanadium 0.7-1.5 niobium up to 0.3 silicon up to 0.03 sulphur up to 0.025 phosphorus balance essentially iron, carbon, nitrogen, vanadium, molybdenum and niobium being intercorrelated by specific ratios, said specific ratios being expressed in atomic fractions through the following mathematical relations:(A) Nb+V/C+N=0.25-0.45 (B) N/C=0.60-1.10 (C) V/Nb=0.50-2.0 (D) Mo/C=0.15-0.25. .Iaddend. 